catena-Poly[[[bis­[2,2′-(propane-1,3-diyl­dithio)bis­(1,3,4-thia­diazole)-κN 4]copper(II)]-bis­[μ-2,2′-(propane-1,3-diyldithio)bis­(1,3,4-thia­diazole)-κ2 N 4:N 4′]] bis­(perchlorate)]

Jian-Hua Qin; Jian-Ge Wang; Pu-Zhou Hu

doi:10.1107/S1600536809006722

. 2009 Feb 28;65(Pt 3):m349–m350. doi: 10.1107/S1600536809006722

catena-Poly[[[bis[2,2′-(propane-1,3-diyldithio)bis(1,3,4-thiadiazole)-κN ⁴]copper(II)]-bis[μ-2,2′-(propane-1,3-diyldithio)bis(1,3,4-thiadiazole)-κ² N ⁴:N ^4′]] bis(perchlorate)]

Jian-Hua Qin ^a,^*, Jian-Ge Wang ^a, Pu-Zhou Hu ^a

PMCID: PMC2968698 PMID: 21582113

Abstract

In the title compound, {[Cu(C₇H₈N₄S₄)₄](ClO₄)₂}_n, the Cu^II atom, occupying a crystallographic inversion centre, is six-coordinated by six N atoms of three symmetry-related 2,2′-(propane-1,3-diyldithio)bis(1,3,4-thiadiazole) (L) ligands in a slightly distorted octahedral geometry. The ligand L adopts two kinds of coordination modes in the crystal structure; one is a monodentate coordination mode and serves to complete the octahedral coordination of the Cu atom and the other is an N:N′-bidentate bridging mode in a trans configuration, bridging Cu atoms via translation symmetry along the b axis into a chain structure. The perchlorate ions serve as acceptors for intermolecular C—H⋯O hydrogen bonds, which link the chains into a three-dimensional network.

Related literature

For Cu—N bonds see, for example: Huang et al. (2009 ▶); Wang et al. (2008 ▶).

Experimental

Crystal data

[Cu(C₇H₈N₄S₄)₄](ClO₄)₂
M _r = 1368.10
Triclinic,
a = 10.321 (3) Å
b = 11.122 (3) Å
c = 12.908 (4) Å
α = 67.213 (3)°
β = 76.602 (3)°
γ = 76.675 (3)°
V = 1312.3 (6) Å³
Z = 1
Mo Kα radiation
μ = 1.22 mm⁻¹
T = 294 K
0.39 × 0.28 × 0.24 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ▶) T _min = 0.646, T _max = 0.756
9833 measured reflections
4857 independent reflections
4081 reflections with I > 2σ(I)
R _int = 0.017

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.110
S = 1.03
4857 reflections
322 parameters
H-atom parameters constrained
Δρ_max = 1.05 e Å⁻³
Δρ_min = −0.50 e Å⁻³

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1997 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809006722/si2158sup1.cif

e-65-0m349-sup1.cif^{(22.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809006722/si2158Isup2.hkl

e-65-0m349-Isup2.hkl^{(237.9KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Selected bond lengths (Å).

Cu1—N1	2.021 (2)
Cu1—N5	2.053 (2)
Cu1—N4ⁱ	2.445 (3)

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Symmetry code: (i) Inline graphic .

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3B⋯O3ⁱⁱ	0.97	2.47	3.357 (6)	153
C7—H7⋯O3ⁱⁱⁱ	0.93	2.51	3.172 (6)	128
C8—H8⋯O4ⁱ	0.93	2.47	3.010 (6)	117
C10—H10A⋯O2^iv	0.97	2.50	3.423 (7)	159
C14—H14⋯O1^v	0.93	2.51	3.419 (7)	167

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) .

Acknowledgments

The authors thank Luoyang Normal University for supporting this work.

supplementary crystallographic information

Comment

The asymmetric structure unit of the title compound consists of a half Cu(II) atom, two [1,3-propanediylbis(thio)]bis[1,3,4-thiadiazole] ligands L, and one perchlorate ion. As depicted in Fig. 1,the Cu(II) atom is coordinated by six N atoms from six ligands L in a slightly distorted octahedral geometry of the central atom. All six Cu—N bond distances are within the range expected for such coordination bonds (Tab. 1) (Huang et al., 2009; Wang et al., 2008). The ligand L adopts two kinds of coordination modes in the crystal structure. One N,N-bidentate bridging mode in trans configuration for bridging the copper atom into a one-dimensional chain, with the bridged Cu-Cu distance of 11.122 (3) Å (Fig. 2). The centroid separation and dihedral angle of thiadiazole rings are 9.131 (2) Å and 74.09 (8) °, respectively. The other thiadiazole ligands adopt monodentate coordination mode and serve to complete the octahedral coordination sphere of the copper atom. The corresponding centroid separation and dihedral angle are 8.1499 (16) Å and 65.04 (12) °, respectively. The region between the chains is taken up by uncoordinated perchlorate ions. The perchlorate ions serve as acceptor for C—H···O hydrogen-bonds, which link the chains into a three-dimensional network (Tab. 2. & Fig. 3).

Experimental

The reaction of [1,3-propanediylbis(thio)]bis[1,3,4-thiadiazole] (0.4 mmol) with Cu(ClO₄)₂ (0.1 mmol) in MeOH(10 ml) for a few minutes afforded a light blue solid, which was filtered, washed with acetone, and dried on air. The single crystals suitable for X-ray analysis were obtained by slow diffusion of Et₂O into the acetonitrile solution of the solid.